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排序方式: 共有132条查询结果,搜索用时 15 毫秒
21.
Marconi N. Peas‐Defrutos Camino Bartolom Max García‐Melchor Pablo Espinet 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3539-3543
By combining kinetic experiments, theoretical calculations, and microkinetic modeling, we show that Pf/Rf (C6F5/C6Cl2F3) exchange between [AuPf(AsPh3)] and trans‐[RhRf(CO)(AsPh3)2] does not occur by typical concerted Pf/Rf transmetalation via electron‐deficient double bridges. Instead, it involves asymmetric oxidative insertion of the RhI complex into the (Ph3As)Au?Pf bond to produce a [(Ph3As)Au?RhPfRf(CO)(AsPh3)2] intermediate, followed by isomerization and reductive elimination of [AuRf(AsPh3)]. Interesting differences were found between the LAu?Ar asymmetric oxidative insertion and the classical oxidative addition process of H2 to Vaska complexes. 相似文献
22.
Brewer CA Brizuela F Wachulak P Martz DH Chao W Anderson EH Attwood DT Vinogradov AV Artyukov IA Ponomareko AG Kondratenko VV Marconi MC Rocca JJ Menoni CS 《Optics letters》2008,33(5):518-520
We have demonstrated near-wavelength resolution microscopy in the extreme ultraviolet. Images of 50 nm diameter nanotubes were obtained with a single ~1 ns duration pulse from a desktop-size 46.9 nm laser. We measured the modulation transfer function of the microscope for three different numerical aperture zone plate objectives, demonstrating that 54 nm half-period structures can be resolved. The combination of near-wavelength spatial resolution and high temporal resolution opens myriad opportunities in imaging, such as the ability to directly investigate dynamics of nanoscale structures. 相似文献
23.
Nonlinear Dynamics - We present an enhanced version of the parametric nonlinear reduced-order model for shape imperfections in structural dynamics we studied in a previous work. In this model, the... 相似文献
24.
Monti S Manet I Manoli F Marconi G 《Physical chemistry chemical physics : PCCP》2008,10(44):6597-6606
In the present contribution we address the study of the interaction of a flavonoid-derivative licochalcone A (LA) with human serum albumin (HSA). The application of circular dichroism, UV-Vis absorption, fluorescence and laser flash photolysis combined with molecular mechanics, molecular dynamics and quantum mechanical calculations of rotational strength afforded a clear picture of the modes of association of the LA neutral molecule to HSA, evidencing specific interactions with protein amino acids and their photophysical consequences. The drug is primarily associated in subdomain IIA where a strong interaction with Trp214 is established. At least two different positions of LA with respect to tryptophan are possible, one with the phenolic ring of the drug facing the aromatic ring of Trp214 and the other with the methoxyphenolic ring of LA in proximity to Trp214. In both cases LA is at ca. 4 angstroms from Trp214. This vicinity does not affect much the S1 singlet state deactivation of the bound drug, which exhibits a slightly higher fluorescence quantum yield and fluorescence lifetime on the order of that of the free molecule. The LA triplet lifetime appears to be somewhat shortened in this site. The secondary binding site is in subdomain IIIA. Here, the carbonyl group of LA experiences a strong H-bond with the OH-phenolic substituent of Tyr411. This interaction reduces substantially the LA molecular degrees of freedom, thereby determining a decrease of both radiative and nonradiative rate constants for decay of the singlet. The overall rigidity of the structure causes a lengthening of the triplet lifetime. 相似文献
25.
Gaining an insight into the photoreactivity of a drug in a protein environment: a case study on nalidixic acid and serum albumin 总被引:1,自引:0,他引:1
Monti S Manet I Manoli F Capobianco ML Marconi G 《The journal of physical chemistry. B》2008,112(18):5742-5754
The binding of nalidixic acid (NA) with human and bovine serum albumin (HSA and BSA) in buffer solution at pH 7.4 was investigated using circular dichroism (CD), UV absorption and fluorescence spectroscopy. Global analysis of multiwavelength spectroscopic data afforded the equilibrium constants of the most stable noncovalent drug/protein adducts of 1:1 and 2:1 stoichiometry and their individual CD, UV absorption, and fluorescence spectra. The primary binding site of the drug was located in subdomain IIIA (Sudlow Site II), whereas the secondary one was assigned to subdomain IIA. Conformational and CD calculations afforded the binding geometries. In the complexes, the fluorescence of the protein was strongly quenched by energy transfer and that of the drug was suppressed by electron transfer. Laser flash photolysis at 355 nm evidenced the formation of a radical pair consisting of a tyroxyl radical (lambdamax = 410 nm) and a reduced nalidixate anion radical NA(2-)* (lambdamax = 640 nm) with quantum yield of 0.4-0.5. Strong evidence was obtained that the process that involves Tyr411 in HSA (Tyr409 in BSA). A further transient with lambdamax approximately 780 nm observed in HSA was attributed to oxidation of the -(S200-S246)- bridge upon electron transfer to NA(-)*. Decay of the confined radical pairs occurred with rates approximately 10(7) s(-1). Formation of covalent drug-protein adducts in mixtures irradiated at lambdairr> 324 nm was proved using HPLC with fluorescence detection. 相似文献
26.
The traditional analysis of the fluorescence recovery kinetics after spot bleaching yields expressions for the diffusion coefficient
of the probe that are not suitable for linear fittings. In a previous work we developed an improved recovery function that
is a better alternative for data analysis. To illustrate its application to real cases and compare it with the previous data
treatment, we measured the time response of fluorescein in aqueous sucrose solutions, covering the unsaturated and the supercooled
region, where decoupling between diffusion and viscosity is observed. The results are compared with the mobility of different
types of solutes in aqueous sucrose solutions and are discussed in terms of the classical hydrodynamic model. 相似文献
27.
Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9912-9923
The underlying conceptual differences in exploiting two- and threefold rotational symmetry in the design of chiral ligands for asymmetric catalysis have been addressed in a comparative study of the catalytic performance of bisoxazoline (BOX) and tris(oxazolinyl)ethanes (trisox) containing copper(II) Lewis acid catalysts. The differences become apparent in constructing new catalysts by systematically "deforming" the stereodirecting ligand by inverting chiral centres or replacing chiral by achiral oxazolines. The catalytic alpha-amination of ethyl 2-methylacetoacetate with dibenzyl azodicaboxylate, which occurs with high enantioselectivity for both Ph(2)-BOX and Ph(3)-trisox copper catalysts, has been employed as the test reaction. In the trisox-copper complex [Cu(II)(iPr(3)-trisox)(kappa(2)-O,O'-MeCOCHCOOEt)](+)[BF(4)](-) (1), which was characterised by X-ray diffraction, two of the oxazoline groups are coordinated to the central copper atom, whilst the third oxazoline unit is dangling with the N-donor pointing away from the metal centre. A similar arrangement is found for the stereochemically "mixed" C(1)-trisox complex [Cu(II){(Ph(3)-trisox(R,S,S)}(kappa(2)-O,O'-MeCOCHCOOEt)(H(2)O)](+)[ClO(4)](-) (2), in which the phenyl substituents adopt a first coordination sphere meso arrangement. The almost identical selectivity of the Ph(3)-trisox(R,R,R)- and Ph(2)-BOX(R,R)-derived catalysts is as expected from the proposed model of the active catalyst based on a partially decoordinated podand. The behaviour of the "desymmetrised" trisox-Cu catalysts may be rationalised in terms of a general steady-state kinetic model for the three possible active bisoxazoline-copper species, which are expected to be in rapid exchange with each other in solution. This applies to both the trisox derivatives with stereochemically inverted and achiral oxazoline rings. The study underscores previous observations of superior performance of the catalysts bearing C(3)-chiral stereodirecting ligands as compared to systems of lower symmetry. 相似文献
28.
29.
Agnello M Belli G Bendiscioli G Bertin A Botta E Bressani T Bruschi M Bussa MP Busso L Calvo D Cereda B Cerello PG Cicalò C Corradini M Costa S De Castro S Donzella A Feliciello A Ferrero L Filippi A Filippini V Fontana A Galli D Garfagnini R Giacobbe B Gianotti P Grasso A Guaraldo C Iazzi F Lanaro A Lodi Rizzini E Lucherini V Marcello S Marconi U Masoni A Minetti B Montagna P Morando M Nichitiu F Panzieri D Pauli G Piccinini M Puddu G Rossetto E Rotondi A Rozhdestvensky AM Saino A Salvini P 《Physical review letters》1995,74(3):371-374
30.
Giancarlo Marconi 《International journal of quantum chemistry》1989,36(3):417-425
The magnetooptical properties (B terms) vibronically induced have been calculated for a series of carbonyl compounds in the region of the first absorption band. The rules deduced experimentally for the signs and sizes of the B terms induced by vibrations of different symmetry are generally confirmed by these calculations. 相似文献